Surface-stabilized anode active material particulates for lithium batteries and production method

Abstract

Provided is a surface-stabilized anode active material particulate (for use in a lithium battery), comprising: (a) one or a plurality of prelithiated or un-prelithiated anode active material particles (with or without a coating of carbon, graphene, or ion-conducting polymer); (b) a protecting polymer layer that wraps around, embraces or encapsulates the one or plurality of anode active material particles, wherein the protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8 S/cm to 5×10 −2 S/cm at room temperature and the protecting polymer layer contains a polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), poly bis-methoxy ethoxyethoxide-phosphazene, polyvinyl chloride, poly(vinylidene chloride), polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), polyethylene glycol (PEG), a PEG derivative, polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, a sulfonated polymer, or a combination thereof.

The invention claimed is: 
     
       1. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
 (a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery, wherein said anode active material particles are prelithiated to contain an amount of lithium from 1% to 100% of a maximum lithium content contained in said anode active material; and 
 (b) a protecting polymer layer that wraps around, embrances or encapsulates said one or plurality of anode active material particles, wherein said protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8  S/cm to 5×10 −2  S/cm at room temperature. 
 
     
     
       2. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material particles are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; ( f ) particles of graphite and carbon; and (g) combinations thereof. 
     
     
       3. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material particles are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm. 
     
     
       4. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material particles contain a sub-micron or micron particle having a dimension, diameter or thickness, from 100 nm to 30 μm. 
     
     
       5. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material particles are coated with a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is disposed between said particle and said protective polymer layer. 
     
     
       6. The surface-stabilized anode active material particulate of  claim 1 , further comprising a layer of carbon, graphene, electron-conducting polymer, or a combination thereof that is coated on said protecting polymer layer. 
     
     
       7. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material comprises silicon and said prelithiated core particle is selected from Li x Si, wherein numerical x is from 0.01 to 4.4. 
     
     
       8. The surface-stabilized anode active material particulate of  claim 1 , wherein said anode active material particles comprise a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants. 
     
     
       9. A mass of anode active material powder comprising the surface-stabilized anode active material particulate of  claim 1 . 
     
     
       10. An anode electrode comprising said surface-stabilized anode active material particulate of  claim 1 , a conductive additive, and a binder. 
     
     
       11. A lithium-ion or lithium metal battery containing the anode electrode of  claim 10 , a cathode electrode, and an electrolyte in ionic contact with the anode electrode and the cathode electrode. 
     
     
       12. A method of producing the surface-stabilized anode active material particulate of  claim 1 , said method comprising:
 (a) providing a plurality of particles of an anode active material; and 
 (b) prelithiating said particles to form prelithiated particles that each contains an amount of lithium from 1% to 100% of a maximum lithium content contained in said anode active material. 
 
     
     
       13. The method of  claim 12 , wherein said anode active material particles are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; (f) particles of graphite and carbon; and (g) combinations thereof. 
     
     
       14. The method of  claim 12 , wherein said step of prelithiating includes electrochemical prelithiation, chemical prelithiation, physical prelithiation, or a combination thereof. 
     
     
       15. The method of  claim 12 , wherein said anode active material comprises silicon and said prelithiated particles comprise a prelithiated silicon Li 4 Si, Li 4.4 Si, or Li x Si, wherein numerical x is from 1 to 4.4. 
     
     
       16. The method of  claim 12 , wherein said step of providing particles of an anode active material comprises providing a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants. 
     
     
       17. The method of  claim 12 , further comprising a step of coating a surface of said prelithiated particles with a thin layer of carbon, graphene, or electron-conducting polymer, having a thickness from 0.5 nm to 1 μm, prior to step (c). 
     
     
       18. The method of  claim 17 , wherein said thin layer of carbon is obtained from pyrolization of a polymer, pitch, or organic precursor or obtained by chemical vapor deposition, physical vapor deposition, or sputtering. 
     
     
       19. A method of producing a lithium-ion battery comprising (A) preparing an anode from the surface-stabilized particles produced by the method of  claim 12 ; and (B) combining said anode with a cathode, and an electrolyte to form said battery. 
     
     
       20. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
 (a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery; and 
 (b) a protecting polymer layer that wraps around, embrances or encapsulates said one or plurality of anode active material particles, wherein said protecting polymer layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8  S/cm to 5×10 −2  S/cm at room temperature. 
 
     
     
       21. The surface-stabilized anode active material particulate of  claim 20 , wherein said anode active material particles are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; ( f ) particles of graphite and carbon; and (g) combinations thereof. 
     
     
       22. The surface-stabilized anode active material particulate of  claim 20 , wherein said anode active material particles are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm. 
     
     
       23. The surface-stabilized anode active material particulate of  claim 20 , wherein said anode active material particles contain a sub-micron or micron particle having a dimension, diameter or thickness, from 100 nm to 30 μm. 
     
     
       24. The surface-stabilized anode active material particulate of  claim 20 , wherein said anode active material particles are coated with a layer of carbon, graphene, electron-conducting polymer, ion-conducting polymer, or a combination thereof that is disposed between said particle and said protective polymer layer. 
     
     
       25. The surface-stabilized anode active material particulate of  claim 20 , further comprising a layer of carbon, graphene, electron-conducting polymer, or a combination thereof that is coated on said protecting polymer layer. 
     
     
       26. The surface-stabilized anode active material particulate of  claim 20 , wherein said anode active material particles comprise a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants. 
     
     
       27. A mass of anode active material powder comprising the surface-stabilized anode active material particulate of  claim 20 . 
     
     
       28. An anode electrode comprising said surface-stabilized anode active material particulate of  claim 20 , a conductive additive, and a binder. 
     
     
       29. A surface-stabilized anode active material particulate for use in a lithium battery, said particulate comprising:
 (a) one or a plurality of anode active material particles capable of reversibly storing lithium ions during a charge or discharge of said battery, wherein said anode active material particles are coated with a layer of carbon, graphene, electron-conducting polymer, or a combination thereof to form one or a plurality of conductive material-coated particles; and 
 (b) a protecting layer that wraps around, embraces or encapsulates said one or plurality of conductive material-coated particles of the anode active material, wherein said protecting layer has a thickness from 0.5 nm to 5 μm, and a lithium ion conductivity from 10 −8  S/cm to 5×10 −2  S/cm at room temperature. 
 
     
     
       30. The surface-stabilized anode active material particulate of  claim 29 , wherein said anode active material particles are selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide, ZnCo 2 O 4 ; ( f ) particles of graphite and carbon; and (g) combinations thereof. 
     
     
       31. The surface-stabilized anode active material particulate of  claim 29 , wherein said anode active material particles are in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm. 
     
     
       32. The surface-stabilized anode active material particulate of  claim 29 , wherein said anode active material particles contain a sub-micron or micron particle having a dimension, diameter or thickness, from 100 nm to 30 μm. 
     
     
       33. A mass of anode active material powder comprising the surface-stabilized anode active material particulate of  claim 29 . 
     
     
       34. An anode electrode comprising said surface-stabilized anode active material particulate of  claim 29 , a conductive additive, and a binder.